Synthesis and characterization of dinuclear monohydro sesquifulvalene complexes with potential NLO properties

E-1-(1″-hydroxycarbonylferrocen-1′-yl)-2-(cycloheptatrienyl)ethene (4) was synthesized by using selective transmetallation reactions. Reaction of 4 with [Cp*Ru(CH3CN)3](PF6) revealed the vinylogue monohydro sesquifulvalene complex E-1-(1″-hydroxycarbonylferrocen-1′-yl)-2-{(1‴-6‴-η-cyclohepta-1‴,3‴,5‴-trien-1‴-yl)(η5-pentamethylcyclopentadienyl)ruthenium(II)}ethene hexafluorophosphate (5). X-ray structure analysis demonstrates that complex 5 crystallizes in the triclinic space group P1¯, which forms discrete dimers via two hydrogen bonds between the carboxylic functions. Reaction of complex 5 with triethylamine or NaHCO3 generated a new organometallic zwitterion E-1-(1″-oxycarbonylferrocen-1′-yl)-2-{(1‴-6‴-η-cyclohepta-1‴,3‴,5‴-trien-1‴-yl)(η5-pentamethylcyclopentadienyl)ruthenium(II)}ethene (6), which was characterized by UV, IR, and NMR spectra.

The monocationic vinylogue monohydro sesquifulvalene complex E-1-(1″-hydroxycarbonylferrocen-1′-yl)-2-{(1‴-6‴-η-cyclohepta-1‴,3‴,5‴-trien-1‴-yl)(η5-pentamethylcyclopentadienyl)ruthenium(II)}ethene hexafluorophosphate (5) was synthesized. After treatment with a base, complex 5 was transformed into the organometallic zwitterion E-1-(1″-oxycarbonylferrocen-1′-yl)-2-{(1‴-6‴-η-cyclohepta-1‴,3‴,5‴-trien-1‴-yl)(η5-pentamethylcyclopentadienyl)ruthenium(II)}ethene (6).Figure optionsDownload as PowerPoint slide